Radiation-Induced Graft Copolymerization Of Butadiene On Polyethylene By Trapped Radicals

The low-temperature grafting of butadiene on polyethylene (PE) preirradiated in air is compared with that on PE preirradiated in vacuo for the effect of several factors on the grafting. Little fundamental difference between the two cases was observed. In both cases the graft conversion curve is trapped radical type and the overall activation energies are 9.7 and 8.4 kcal/mol for 0.947-density PE and 0.916-density PE, respectively. Percent grafting is proportional to the square root of the dose rate (= total dose). The retarding effect of oxygen at irradiation or storage after irradiation on the grafting scarcely appears when the irradiation temperature or storage temperature is below 15°C. For thinner film and lower density of PE this effect appears clearly at the higher temperature. Therefore, it may be concluded that the low-temperature grafting of butadiene onto PE preirradiated in air is initiated predominantly by nonoxidized radical (allyl radical) trapped in PE and that the grafting reaction occurs in the semicrystalline part of PE.